EP1006097B1 - Procédé d'oligomérisation - Google Patents

Procédé d'oligomérisation Download PDF

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Publication number
EP1006097B1
EP1006097B1 EP99309287A EP99309287A EP1006097B1 EP 1006097 B1 EP1006097 B1 EP 1006097B1 EP 99309287 A EP99309287 A EP 99309287A EP 99309287 A EP99309287 A EP 99309287A EP 1006097 B1 EP1006097 B1 EP 1006097B1
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Prior art keywords
oligomers
concentration
oligomerization
preselected
tetramers
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Expired - Lifetime
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EP99309287A
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German (de)
English (en)
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EP1006097A1 (fr
Inventor
Allen David Strebel
Jeffrey Robert Wolf
William Lee Cox
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Ineos USA LLC
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BP Corp North America Inc
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/14—Catalytic processes with inorganic acids; with salts or anhydrides of acids
    • C07C2/20—Acids of halogen; Salts thereof ; Complexes thereof with organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/06—Halogens; Compounds thereof
    • C07C2527/08—Halides
    • C07C2527/12—Fluorides
    • C07C2527/1213—Boron fluoride
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S585/00—Chemistry of hydrocarbon compounds
    • Y10S585/8995—Catalyst and recycle considerations
    • Y10S585/903—Catalyst and recycle considerations with hydrocarbon recycle to control synthesis reaction, e.g. by cooling, quenching

Definitions

  • the present invention relates to a process for the oligomerization of an acyclic monoolefin monomer and more particularly concerns the control of the oligomerization reaction to produce predetermined relative amounts of at least two preselected oligomers in a higher boiling fraction of the oligomerization products and the recycle of a lower boiling fraction of the oligomerization products.
  • the subsequent oligomerization essentially completely converts the C 8 -C 12 ⁇ -olefin and converts the low viscosity unsaturated trimer to an oligomerization product from which dimer and any unreacted C 8 -C 12 ⁇ -olefin monomer are removed.
  • the remaining oligomerization product has a medium viscosity.
  • Nipe et al. U.S. Patent No. 4,225,739, issued on September 30, 1980, discloses that light boiling fractions of the oligomerization product are recycled to the oligomerization step in order to increase the yield of the desired heavier oligomerization product, hopefully without degrading the physical properties of the finished product.
  • the patent reports that, in the oligomerization of short chain and long chain 1-olefins in the presence of Friedel-Crafts catalysts to produce super-quality synthetic lubricants, the use of recycle with catalysts such as aluminum chloride did increase the ultimate yield, but the physical properties were either unfavorable or showed little change compared with the properties obtained when recycle was not employed.
  • Nipe et al. discloses that when a boron trifluoride catalyst promoted by either water or alcohol was employed, the product yield was essentially unchanged from the yield when recycle was not employed, but the fluid viscosity decreased markedly accompanied by an improvement in viscosity index.
  • Nipe et al. discloses a process for producing lubricants having a low viscosity and a high viscosity index that comprises oligomerizing a mixture of short-chain 1-olefins, long chain 1-olefins, and low-boiling recycle from a previous oligomerization run in the presence of boron trifluoride catalyst promoted with water or alcohol.
  • the recycle employed is obtained from a previous oligomerization run and is the overhead fluid fraction obtained when the total oligomerization product is topped to meet a flash point of at least 400°F.
  • US 4,239,940 discloses a continuous oligomerization process employing a loop recycle reactor for the oligomerization of alpha-olefin. However, the process is directed to providing synthetic lubricant products with a predominance of trimer and tetramer, and especially a high trimer to tetramer concentration ratio, i.e. 2.5:1 to 3:1, with 3.98:1 being the highest trimer to tetramer ratio achieved in the exemplified reactions.
  • a synthetic lubricant having a particular predetermined kinematic viscosity can be produced by employing particular oligomer concentration ratios, e.g. trimers to tetramers.
  • US 4,239,940 does not mention the kinematic viscosities of the products obtained therein.
  • European Patent Application No. 95106749.5 filed May 4, 1995 and published November 8, 1995, discloses a process for the oligomerization of alpha-olefin monomer in which the oligomerization product is fractionated and unreacted alpha-olefin monomer and a portion of the dimers and trimers in the product are separated and recycled to the oligomerization step.
  • the patent application states that the use of recycle in the process results in an improvement in the yield of the higher oligomeric product and permits product properties to be adapted to the respective requirements.
  • the higher boiling fractions of a number of oligomerization product mixtures can be characterized by their properties and by their compostions. More particularly, the compositions of such higher boiling fractions can be characterized in terms of the presence of certain oligomers in them, the relative concentrations of such certain oligomers in the higher boiling fractions, and the combined concentrations of such certain oligomers in the higher boiling fraction. Therefore, by producing an oligomerization product whose higher boiling fraction has a specific desired aforesaid characterization it is possible to produce a higher boiling fraction which in its entirety has a desired set of properties and can be employed directly in or as a synthetic lubricating oil, without any further adjustments of the composition of the higher boiling fraction by the addition of components to or the removal. of components from the higher boiling fraction.
  • an oligomerization product whose higher boiling fraction has a certain desired set of properties can be produced highly selectively by conducting the oligomerization reaction under conditions of reaction temperature, pressure, catalyst system composition and concentration and reaction time such that at least two desired oligomers--referred to hereafter as preselected oligomers--are produced and present in the higher boiling fraction, such that the ratio of the concentrations of the at least two preselected oligomers in the mixture of oligomers produced having molecular weights at least as large as the lowest molecular weight of the preselected oligomers is within a predetermined range of values therefor and such that in combined concentrations of the preselected oligomers comprises at least 60 weight percent of the oligomers produced having molecular weights at least as large as the lowest molecular weight of the preselected oligomers.
  • the oligomerization catalyst system comprises a Friedel-Crafts catalyst and a promoter.
  • Representative Friedel-Crafts catalysts are BF 3 , BCl 3 , AlCl 3 , AlBr 3 , SnCl 4 , GaCl 3 , FeBr 3 , and the like.
  • the catalyst is BF 3 .
  • promoters include water, silica gel, aliphatic ethers such as dimethyl ether and diethyl ether, aliphatic alcohols such as methanol, ethanol, propanol, and n-butanol, polyols such as ethylene glycol and glycerol, aliphatic carboxylic esters, ketones, aldehydes and acid anhydrides.
  • the promoter is n-butanol, n-propanol or water.
  • the amount of Friedel-Crafts catalyst employed in the method of this invention should be a catalytic amount, that is an amount which when employed in the presence of a promoter will cause the reaction to proceed at a reasonable rate.
  • a useful of amount of Friedel-Crafts catalyst in the method of this invention is in the range of from about 0.0001 moles, preferably from 0.005 moles, to 0.20 moles, preferably to 0.03 moles of catalyst per mole of 1-decene employed.
  • the amount of promoter employed in the method of this invention is in the range of from 0.0001 moles, preferably from 0.0025 moles, to 0.20 moles, preferably to 0.025 moles per mole of 1-decene employed.
  • the oligomerization reaction is conducted at a temperature in the range of from 0°C, preferably from 20°C, to 100°C, preferably to 60°C, and at a pressure in the range of from 0 kPa (0 psig), preferably from 34 kPa (5 psig), to 5 MPa (725 psig), preferably to 0.34 MPa (50 psig).
  • the dimers and trimers are the preselected oligomers, and the oligomerization is conducted such that the ratio of the concentration of trimers to the concentration of dimers in the mixture of oligomers produced is less than 0.15, preferably less than 0.1.
  • the trimers and tetramers are the preselected oligomers, and the oligomerization is conducted such that the ratio of the concentration of tetramers to the concentration of trimers in the mixture of oligomers produced is (a) less than 0.25, preferably less than 0.23 and (b) greater than 0.1, preferably greater than 0.16.
  • the trimers, tetramers and pentamers are the preselected oligomers, and the oligomerization is conducted such that the ratio of the concentration of pentamers to the concentration of tetramers in the mixture of oligomers produced is (a) less than 0.55, preferably less than 0.30, and (b) greater than 0.15, preferably greater than 0.2, and the ratio of the concentration of trimers to the concentration of tetramers is (a) less than 0.9, preferably less than or equal to 0.76, and (b) greater than 0.55, preferably greater than 0.6.
  • the trimers, tetramers and pentamers are the preselected oligomers, and the oligomerization is conducted such that the ratio of the concentration of pentamers to the concentration of tetramers in the mixture of oligomers produced is (a) less than 0.65, preferably less than 0.6, and (b) greater than 0.45, preferably greater than 0.5, and the ratio of the concentration of trimers to the concentration of tetramers is (a) less than 0.25, preferably less than or equal to 0.20, and (b) greater than 0.08, preferably greater than 0.12.
  • the trimers, tetramers and pentamers are the preselected oligomers, and the oligomerization is conducted such that the ratio of the concentration of pentamers to the concentration of tetramers in the mixture of oligomers produced is (a) less than 1.0, preferably less than 0.90, and (b) greater than 0.65, preferably greater than 0.75, and the ratio of the concentration of trimers to the concentration of tetramers is (a) less than 0.10, preferably preferably less than or equal to 0.05, and (b) greater than 0.0, preferably greater than 0.01.
  • the oligomerization reaction is terminated either before the aforesaid ratio of the aforesaid concentrations of the at least two preselected oligomers falls outside the aforesaid range of values therefor, or before the combination of such at least two preselected oligomers comprises less than 60 weight percent of the fraction of oligomers produced having molecular weights at least at large as the molecular weights of such at least two oligomers.
  • the reaction is terminated and the Friedel-Crafts catalyst system is removed from the oligomerization product. This can be done by any convenient conventional technique, for example, by washing with water or aqueous ammonia.
  • the lower boiling fraction is then removed from the oligomerization product, for example, by distillation.
  • the lower boiling fraction comprises unreacted monomer, oligomers having lower molecular weights than the lowest molecular weight of the preselected oligomers, and optionally a minor portion (that is, less than 15 weight percent, preferably less than 5 weight percent) of the oligomers having molecular weights at least as large as the lowest molecular weight of the preselected oligomers.
  • At least a portion of the separated lower boiling fraction is returned to the oligomerization reactor as the aforesaid recycled fraction.
  • the weight ratio of recycled fraction to fresh monoolefin monomer fed to the oligomerization step is typically in the range of from 0.1, preferably from 0.25, to 5.0, preferably to 4.0.
  • the distillation conditions employed are such as to remove as bottom fraction a higher boiling fraction that comprises a major portion (that is, at least 85 weight percent, preferably at least 95 weight percent) of the oligomers having molecular weights at least as large as the lowest molecular weight of the preselected oligomers.
  • the higher boiling fraction is the synthetic hydrocarbon product of the method of this invention and has the desired physical characteristics for use as or in a synthetic lubricating oil having specific desired properties.
  • the distillation conditions employed are not intended to effect a change in the composition of the higher boiling fraction.
  • the following example illustrates a low conversion oligomerization of 1-decene and recycle of the undesired light cut to maximize production of the desired heavy cut oligomer distribution.
  • the desired product was an oligomer distribution high in C 30 olefin content.
  • a multipass batch synthesis was used to simulate a continuous recycle process as follows:
  • the following example illustrates a low conversion oligomerization of 1-decene and recycle of the undesired light cut to maximize production of the desired heavy cut oligomer distribution.
  • the desired product was an oligomer distribution high in C 30 oligomer content.
  • a multipass semi-continuous synthesis was used to simulate a continuous recycle process, as follows:
  • the following example illustrates a variable study for low conversion oligomerization of 1-decene and recycle of the undesired light cut to maximize production of the desired heavy cut oligomer distribution.
  • the desired product was an oligomer distribution high in C 30 olefin content.
  • the purpose of this experiment was to demonstrate a range of possible conditions and optimize those conditions for the desired C 30 olefin selectivity.
  • the following example illustrates a high conversion oligomerization of 1-decene to produce a normal oligomer distribution.
  • the desired product was an oligomer distribution high in C 30 olefin content
  • the purpose of this example is to demonstrate the advantage of the low conversion with recycle process over the high conversion process to selectively generate the C 30 oligomer.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Lubricants (AREA)
  • Polymerisation Methods In General (AREA)
  • Polymerization Catalysts (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Claims (8)

  1. Procédé pour produire un hydrocarbure synthétique ayant une viscosité cinématique prédéterminée à 100°C de 2 x 10-6 m2.s-1, 4 x 10-6 m2.s-1, 6 x 10-6 m2.s-1, 8 x 10-6 m2.s-1 ou 10-5 m2.s-1 (2, 4, 6, 8 ou 10 cSt) et ayant une composition prédéterminée comprenant :
    l'oligomérisation du 1-décène en présence d'une fraction recyclée et d'un système de catalyseur d'oligomérisation, dans des conditions réactionnelles de température comprise dans la plage allant de 0°C à 100°C, de pression comprise dans la plage allant de 0 à 5 MPa (0 psig à 725 psig), avec un système de catalyseur comprenant un catalyseur Friedel-Crafts dans la plage allant de 0,0001 à 0,20 mole par mole de 1-décène, et un promoteur dans la plage allant de 0,0001 à 0,20 mole par mole de 1-décène et un temps de réaction, ceux-ci étant choisis de telle façon que le ratio des concentrations d'au moins deux oligomères présélectionnés dans le mélange des oligomères produits ayant des masses moléculaires au moins aussi grandes que la plus basse masse moléculaire de tels oligomères présélectionnés soit compris dans une plage de valeurs prédéterminée pour celui-ci, et que la concentration combinée d'au moins deux oligomères présélectionnés comprenne au moins 60 pour cent en poids de ces oligomères produits ayant des masses moléculaires au moins aussi grandes que la plus basse masse moléculaire de tels oligomères présélectionnés ;
    la séparation du catalyseur du mélange de produit et l'arrêt de l'oligomérisation, soit avant que le ratio des concentrations susmentionnées au moins deux oligomères présélectionnés susmentionnés tombe en dehors de la plage de valeurs prédéterminée pour celui-ci, soit avant que la concentration combinée d'au moins deux oligomères présélectionnés comprenne moins de 60 pour cent en poids de ces oligomères produits ayant des masses moléculaires au moins aussi grandes que la plus basse masse moléculaire de tels au moins deux oligomères ;
    la séparation du mélange du produit d'oligomérisation en (a) une fraction d'ébullition inférieure comprenant le 1-décène non-réagi, les oligomères ayant des masses moléculaires plus basses que la plus basse masse moléculaire des tels oligomères présélectionnés, et facultativement moins de 15 pour cent en poids d'oligomères ayant des masses moléculaires au moins aussi grandes que la plus basse masse moléculaire des oligomères présélectionnés et (b) une fraction d'ébullition supérieure constituée par le produit hydrocarbure synthétique et comprenant au moins 85 pour cent en poids des oligomères ayant des masses moléculaires au moins aussi grandes que la plus basse masse moléculaire des oligomères présélectionnés ; et
    le recyclage vers l'étape d'oligomérisation d'au moins une partie de la fraction du point d'ébullition inférieure séparée susmentionnée qui constitue la fraction recyclée susmentionnée ;
       dans laquelle :
    a) lorsque la viscosité cinématique prédéterminée est de 2 x 10-6 m2.s-1 (2 cSt), les dimères et trimères sont les oligomères présélectionnés susmentionnés, et l'oligomérisation est conduite de telle façon que le ratio de la concentration en trimères sur la concentration en dimères dans le mélange des oligomères produits soit inférieure à 0,15 ;
    b) lorsque la viscosité cinématique prédéterminée est de 4 x 10-6 m2.s-1 (4 cSt), les trimères et tétramères sont les oligomères présélectionnés susmentionnés, et l'oligomérisation est conduite de telle façon que le ratio de la concentration en tétramères sur la concentration en trimères dans le mélange des oligomères produits soit inférieur à 0,23 et supérieur à 0,1 ;
    c) lorsque la viscosité cinématique prédéterminée est de 6 x 10-6 m2.s-1 (6 cSt), les trimères, tétramères et pentamères sont les oligomères présélectionnés susmentionnés, et l'oligomérisation est conduite de telle façon que le ratio de la concentration en pentamères sur la concentration en tétramères dans le mélange des oligomères produits soit inférieur à 0,55 et supérieur à 0,15, et de telle façon que le ratio de la concentration en trimères sur la concentration en tétramères soit inférieur à 0,9 et supérieur à 0,55 ;
    d) lorsque la viscosité cinématique prédéterminée est de 8 x 10-6 m2.s-1 (8 cSt), les trimères, tétramères et pentamères sont les oligomères présélectionnés susmentionnés, et l'oligomérisation est conduite de telle façon que le ratio de la concentration en pentamères sur la concentration en tétramères dans le mélange des oligomères produits soit inférieur à 0,65 et supérieur à 0,45 et de telle façon que le ratio de la concentration en trimères sur la concentration en tétramères soit inférieur à 0,25 et supérieur à 0,08 ; et
    e) lorsque la viscosité cinématique prédéterminée est de 10-5 m2.s-1 (10 cSt), les trimères, tétramères et pentamères sont les oligomères présélectionnés susmentionnés, et l'oligomérisation est conduite de telle façon que le ratio de la concentration en pentamères sur la concentration en tétramères dans le mélange des oligomères produits soit inférieur à 1,0 et supérieur à 0,65 et de telle façon que le ratio de la concentration en trimères sur la concentration en tétramères soit inférieur à 0,10 et supérieur à 0,0.
  2. Procédé selon la revendication 1, dans lequel le catalyseur Friedel-Crafts est compris dans la plage allant de 0,005 mole à 0,03 mole de catalyseur par mole de 1-décène.
  3. Procédé selon la revendication 1 ou la revendication 2, dans lequel la quantité de promoteur employée est compris dans la plage allant de 0,0025 mole à 0,025 mole par mole de 1-décène.
  4. Procédé selon l'une quelconque des revendications précédentes, dans lequel le système de catalyseur d'oligomérisation comprend un catalyseur BF3 et un promoteur de catalyseur.
  5. Procédé selon la revendication 4, dans lequel le promoteur est un alcool aliphatique, un polyol aliphatique, un éther aliphatique, un ester carboxylique aliphatique, une cétone, un aldéhyde ou un anhydride d'acide ou de l'eau.
  6. Procédé selon la revendication 5, dans lequel le promoteur est un alcool primaire linéaire ou de l'eau.
  7. Procédé selon l'une quelconque des revendications précédentes, dans lequel l'oligomérisation est effectuée à une température comprise dans la plage allant de 20°C à 60°C.
  8. Procédé selon l'une quelconque des revendications précédentes, dans lequel l'oligomérisation est effectuée à une pression comprise dans la plage allant de 34,5 kPa à 344,5 kPa (jauge de 5 à 50 livres par pouce carré).
EP99309287A 1998-11-30 1999-11-22 Procédé d'oligomérisation Expired - Lifetime EP1006097B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US09/201,514 US6147271A (en) 1998-11-30 1998-11-30 Oligomerization process
US201514 2002-07-23

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EP1006097A1 EP1006097A1 (fr) 2000-06-07
EP1006097B1 true EP1006097B1 (fr) 2003-07-09

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US (1) US6147271A (fr)
EP (1) EP1006097B1 (fr)
JP (1) JP5036927B2 (fr)
CA (1) CA2290874C (fr)
DE (1) DE69909410T2 (fr)

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DE69909410T2 (de) 2004-04-22
CA2290874C (fr) 2009-04-14
US6147271A (en) 2000-11-14
DE69909410D1 (de) 2003-08-14
JP5036927B2 (ja) 2012-09-26
CA2290874A1 (fr) 2000-05-30
JP2000159832A (ja) 2000-06-13

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